Dielectric ceramic composition

ABSTRACT

A dielectric ceramic composition having a high relative dielectric constant a high quality factor and a small temperature coefficient of resonance frequency, consisting essentially of calcium oxide, strontium, oxide, bismuth oxide and titanium oxide, and having a composition represented by the formula: 
     
         (CaO).sub.a.(SrO).sub.b.(Bi.sub.2 O.sub.3).sub.c.(TiO.sub.2).sub.d 
    
     wherein 0≦a&lt;30, 0&lt;b≦20, 10≦c≦50, 40≦d≦80, and 0&lt;a+b≦30 by mol %. 
     This composition may contain at least one of thallium oxide, yttrium oxide and manganese oxide and at least one of germanium oxide, zirconium oxide, tin oxide, cerium oxide and hafnium oxide.

BACKGROUND OF THE INVENTION

The present invention relates to a dielectric ceramic composition having a high relative dielectric constant (εr) and a small and widely controllable temperature coefficient of resonance frequency (τf).

Recently, ceramic filters have been widely used for movable radio transmitters and receivers such as automobile telephones and cordless telephones operable at microfrequency bands from MHz to GHz. This is due to the fact that the dielectric materials constituting the ceramic filters have high dielectric constants (εr) and quality factors Q under no load (Q₀), and that their temperature coefficients (τf) of resonance frequency are freely controllable on both the positive and the negative sides from 0 by changing the compositions of the dielectric materials.

Conventional dielectric materials are, for instance, MgO--CaO--TiO₂, ZrO₂ --TiO₂ --SnO₂, and BaO--TiO₂ -lanthanoid oxide, etc.

However, these dielectric materials have relative dielectric constants (εr) less than 100, and the miniaturization of resonance elements formed from them is inherently limited.

Therefore, there is a strong desire for dielectric ceramic compositions with high relative dielectric constants (εr).

SUMMARY OF THE INVENTION

As a result of intense research directed toward developing a dielectric ceramic composition having a relative dielectric constant (εr) of 100 or more, a temperature coefficient (τf) of ±100 ppm/°C. or less and a quality factor under no load (Q₀) of 100 or more, the inventors have found that the above properties can be obtained when the dielectric ceramic composition has a composition represented by the formula:

    (CaO).sub.a.(SrO).sub.b.(Bi.sub.2 O.sub.3).sub.c.(TiO.sub.2).sub.d

wherein 0≦a<30, 0<b≦20, 10≦c≦50, 40≦d≦80, and 0<a+b≦30 by mol %.

DETAILED DESCRIPTION OF THE INVENTION

According to a first embodiment of the present invention, the dielectric ceramic composition is represented by the general formula:

    (CaO).sub.a.(SrO).sub.b.(Bi.sub.2 O.sub.3).sub.c.(TiO.sub.2).sub.d

wherein 0≦a<30, 0<b≦20, 10≦c≦50, 40≦d≦80, and 0<a+b≦30 by mol %.

When the contents of CaO, SrO, Bi₂ O₃ and TiO₂ are not in the above composition ranges, the Q₀ becomes less than 100, so that the dielectric ceramic composition is unsuitable for practical applications.

The preferred contents of CaO, SrO, Bi₂ O₃ and TiO₂ are 0≦a≦10, 5≦b≦15, 25≦c≦30, 50≦d≦60 and 5≦a+b≦20 by mol %.

The dielectric ceramic composition according to a second embodiment of the present invention has a main composition represented by the general formula:

    (CaO).sub.a.(SrO).sub.b.(Bi.sub.2 O.sub.3).sub.c.(TiO.sub.2).sub.d

wherein 0≦a<30, 0<b≦20, 10≦c≦50, 40≦d≦80, and 0<a+b≦30 by mol %, and further contains at least one of the following components:

5 weight % or less of thallium oxide (Tl₂ O₃),

5 weight % or less of yttrium oxide (Y₂ O₃), and

0.6 weight % or less of manganese oxide (MnO).

When Tl₂ O₃ exceeds 5 weight %, the Q₀ becomes less than 100, and the τf becomes largely negative. And when Y₂ O₃ exceeds 5 weight %, or when MnO exceeds 0.6 weight %, similar problems take place, providing ceramic materials unsuitable for practical applications.

The preferred contents of CaO, SrO, Bi₂ O₃ and TiO₂ are 0≦a≦10, 5≦b≦15, 25≦c≦30, 50≦d≦60 and 5≦a+b≦20 by mol %, and the total amount of Tl₂ O₃, Y₂ O₃ and MnO is preferably 2 weight % or less.

The dielectric ceramic composition according to a third embodiment of the present invention has a composition represented by the general formula:

    (CaO).sub.a.(SrO).sub.b.(Bi.sub.2 O.sub.3).sub.c.(TiO.sub.2).sub.d.(RO.sub.2).sub.e

wherein R represents at least one of Ge, Zr, Sn, Ce and Hf, and a, b, c, d and e satisfy 0≦a<30, 0<b≦20, 10≦c≦50, 40≦d≦80, 0<e<5, and 0<a+b≦30 by mol %.

When GeO₂, ZrO₂, SnO₂, CeO₂ and HfO₂ reach 5 mol %, the Q₀ becomes less than 100, and the τf cannot be detected at high temperatures because measured peaks are concealed by noises or become increasingly negative, making the dielectric ceramic composition unsuitable for practical applications.

The preferred contents of CaO, SrO, Bi₂ O₃ and TiO₂ are 0≦a≦10, 5≦b≦15, 25≦c≦30, 50≦d≦60 and 5≦a+b≦20 by mol %, and RO₂ is preferably 2 mol % or less.

The dielectric ceramic composition of the present invention can be prepared by mixing and sintering starting material powders in the predetermined proportions. The starting materials may be carbonates, nitrates, organic acid salts, etc. because they are thermally decomposed to form the corresponding oxides.

EXAMPLE 1

CaCO₃ powder, SrCO₃ powder, Bi₂ O₃ powder and TiO₂ powder were introduced into a polyethylene pot in the proportions as shown in Table 1 together with agate balls and acetone, and mixed for 16 hours.

The resulting slurry was dried by heating and classified with a 5-mesh sieve, and then burned at 1000° C. for 2 hours in the air. The burned product was again introduced into the polyethylene pot containing agate balls together with acetone and pulverized for 16 hours.

The resulting slurry was dried by heating, mixed with a polyvinyl alcohol aqueous solution, and then granulated with a 32-mesh sieve.

The granulated powder was pressed at 1 ton/cm², and sintered in the atmosphere at 1200°-1400° C. for 4 hours. The resulting sintered product was worked to have a diameter of about 30 mm and a height of about 15 mm. This sample was measured at about 1 GHz to obtain a peak in a TE₀₁₁ mode, and the sample's εr and Q₀ were calculated from the above peak. Next, the τf was determined from the variation or resonance frequency between -20° C. and +60° C. The results are shown in Table 1.

                  TABLE 1                                                          ______________________________________                                         Sample Composition (mol %)         τf                                      No.    CaO    SrO    Bi.sub.2 O.sub.3                                                                     TiO.sub.2                                                                           εr                                                                          Q.sub.0                                                                              (ppm/°C.)                    ______________________________________                                         1      0      14.29  28.57 57.14                                                                               198  168   -30                                 2      1      13.29  28.57 57.14                                                                               196  182   -10                                 3      2      12.29  28.57 57.14                                                                               192  188   +1                                  4      2.86   11.43  28.57 57.14                                                                               188  196   +18                                 5      4      10.29  28.57 57.14                                                                               184  200   +40                                 6      5      9.29   28.57 57.14                                                                               180  210   +62                                 7      5.71   8.57   28.57 57.14                                                                               176  230   +75                                 8      6      8.29   28.57 57.14                                                                               177  220   +80                                 9      6.5    7.79   28.57 57.14                                                                               176  220   +84                                 10     20     10     40    30   169  53    +30                                 11     5      25     20    50   150  90    +42                                 12     10     10     5     75   120  95    +320                                ______________________________________                                          Note:                                                                          Sample Nos. 1-9: Examples of the present invention                             Sample Nos. 10-12: Comparative Examples                                  

EXAMPLE 2

CaCO₃ powder, SrCO₃ powder, Bi₂ O₃ powder, TiO₂ powder, Tl₂ O₃ powder, Y₂ O₃ powder and MnCO₃ powder were introduced into a polyethylene pot in the proportions as shown in Table 2 together with agate balls and acetone, and mixed for 16 hours.

The resulting slurry was dried by heating and classified with a 5-mesh sieve, and then burned at 1000° C. for 2 hours in the air. The burned product was again introduced into the polyethylene pot containing agate balls together with acetone and pulverized for 16 hours.

The resulting slurry was dried by heating, mixed with a polyvinyl alcohol aqueous solution, and then granulated with a 32-mesh sieve.

The granulated powder was pressed at 1 ton/cm², and sintered in the atmosphere at 1200°-1400° C. for 4 hours. The resulting sintered product was worked to have a diameter of about 30 mm and a height of about 15 mm. This sample was measured at about 1 GHz to obtain a peak in a TE₀₁₁ mode, and the sample's εr and Q₀ were calculated from the above peak. Next, the τf was determined from the variation of resonance frequency between -20° C. and +60° C. The results are shown in Table 2.

                                      TABLE 2                                      __________________________________________________________________________     Sample                                                                              Composition (mol %)                                                                         Additives    τf                                          No.  CaO                                                                               SrO                                                                               Bi.sub.2 O.sub.3                                                                   TiO.sub.2                                                                          (weight %)                                                                           εr                                                                        Q.sub.0                                                                           (ppm/°C.)                                __________________________________________________________________________     1    2.86                                                                              11.43                                                                             28.57                                                                              57.14                                                                             Tl.sub.2 O.sub.3                                                                   0.1                                                                               187                                                                               174                                                                               -6                                              2    2.86                                                                              11.43                                                                             28.57                                                                              57.14                                                                             Tl.sub.52 O.sub.3                                                                  1.0                                                                               188                                                                               179                                                                               -9                                              3    4.0                                                                               10.29                                                                             28.57                                                                              57.14                                                                             Tl.sub.2 O.sub.3                                                                   3.0                                                                               184                                                                               200                                                                               +5                                              4    2.86                                                                              11.43                                                                             28.57                                                                              57.14                                                                             Y.sub.2 O.sub.3                                                                    0.5                                                                               179                                                                               163                                                                               +7                                              5    2.86                                                                              11.43                                                                             28.57                                                                              57.14                                                                             MnO 0.006                                                                             188                                                                               203                                                                               +1                                              6    4.0                                                                               10.29                                                                             28.57                                                                              57.14                                                                             MnO 0.003                                                                             184                                                                               220                                                                               +5                                              7    2.86                                                                              11.43                                                                             28.57                                                                              57.14                                                                             Y.sub.2 O.sub.3                                                                    3.0                                                                               169                                                                               138                                                                               +2                                              8    4.0                                                                               10.29                                                                             28.57                                                                              57.14                                                                             Tl.sub.2 O.sub.3                                                                   1.0                                                                               185                                                                               170                                                                               +3                                                                MnO 0.006                                                    9    2.86                                                                              11.43                                                                             28.57                                                                              57.14                                                                             Y.sub.2 O.sub.3                                                                    0.5                                                                               180                                                                               199                                                                               +2                                                                MnO 0.006                                                    10   2.86                                                                              11.43                                                                             28.57                                                                              57.14                                                                             Tl.sub.2 O.sub.3                                                                   1.0                                                                               182                                                                               179                                                                               -1                                                                Y.sub.2 O.sub.3                                                                    0.1                                                      11   2.86                                                                              11.43                                                                             28.57                                                                              57.14                                                                             Tl.sub.2 O.sub.3                                                                   0.05                                                                              185                                                                               186                                                                               -2                                                                Y.sub.2 O.sub.3                                                                    0.1                                                      12   2.86                                                                              11.43                                                                             28.57                                                                              57.14                                                                             Tl.sub.2 O.sub.3                                                                   6.0                                                                               179                                                                               90 -22                                             13   2.86                                                                              11.43                                                                             28.57                                                                              57.14                                                                             Y.sub.2 O.sub.3                                                                    6.0                                                                               142                                                                               89 -48                                             14   2.86                                                                              11.43                                                                             28.57                                                                              57.14                                                                             MnO 0.9                                                                               186                                                                               85 -52                                             __________________________________________________________________________      Note:                                                                          Sample Nos. 1-11: Examples of the present invention                            Sample Nos. 12-14: Comparative Examples                                  

EXAMPLE 3

CaCO₃ powder, SrCO₃ powder, Bi₂ O₃ powder, TiO₂ powder, GeO₂ powder, ZrO₂ powder, SnO₂ powder, CeO₂ powder and HfO₂ powder were introduced into a polyethylene pot in the proportions as shown in Table 3 together with agate balls and acetone, and mixed for 16 hours.

The resulting slurry was dried by heating and classified with a 5-mesh sieve, and then burned at 1000° C. for 2 hours in the air. The burned product was again introduced into the polyethylene pot containing agate balls together with acetone and pulverized for 16 hours.

The resulting slurry was dried by heating, mixed with a polyvinyl alcohol aqueous solution, and then granulated with a 32-mesh sieve.

The granulated powder was pressed at 1 ton/cm², and sintered in the atmosphere at 1200°-1400° C. for 4 hours. The resulting sintered product was worked to have a diameter of about 30 mm and a height of about 15 mm. This sample was measured at about 1 GHz to obtain a peak in a TE₀₁₁ mode, and the sample's εr and Q₀ were calculated from the above peak. Next, the τf was determined from the variation of resonance frequency between -20° C. and +60° C. The results are shown in Table 3.

                                      TABLE 3                                      __________________________________________________________________________     Sample                                                                             Composition (mol %)          τf                                        No. CaO                                                                               SrO Bi.sub.2 O.sub.3                                                                   TiO.sub.2                                                                           RO.sub.2                                                                             εr                                                                        Q.sub.0                                                                            (ppm/°C.)                              __________________________________________________________________________     1   2.86                                                                              11.43                                                                              28.57                                                                              57.04                                                                              GeO.sub.2                                                                          0.1                                                                               186                                                                               179 -5                                            2   2.86                                                                              11.43                                                                              28.57                                                                              56.14                                                                              GeO.sub.2                                                                          1.0                                                                               181                                                                               166 -15                                           3   2.86                                                                              11.43                                                                              28.57                                                                              56.64                                                                              ZrO.sub.2                                                                          0.5                                                                               185                                                                               170 +2                                            4   2.86                                                                              11.43                                                                              28.57                                                                              56.14                                                                              ZrO.sub.2                                                                          1.0                                                                               181                                                                               140 -12                                           5   2.86                                                                              11.43                                                                              28.57                                                                              57.06                                                                              SnO.sub.2                                                                          0.08                                                                              188                                                                               175 +8                                            6   2.86                                                                              11.43                                                                              28.57                                                                              56.14                                                                              SnO.sub.2                                                                          1.0                                                                               175                                                                               133 -60                                           7   2.86                                                                              11.43                                                                              28.57                                                                              56.54                                                                              CeO.sub.2                                                                          0.6                                                                               186                                                                               192 -1                                            8   2.86                                                                              11.43                                                                              28.57                                                                              56.14                                                                              CeO.sub.2                                                                          1.0                                                                               182                                                                               191 -16                                           9   2.86                                                                              11.43                                                                              28.57                                                                              56.64                                                                              HfO.sub.2                                                                          0.5                                                                               182                                                                               165 +2                                            10  2.86                                                                              11.43                                                                              28.57                                                                              56.14                                                                              HfO.sub.2                                                                          1.0                                                                               178                                                                               138 -54                                           11  5.0                                                                               9.29                                                                               28.57                                                                              56.14                                                                              GeO.sub.2                                                                          1.0                                                                               179                                                                               205 +4                                            12  2.86                                                                              11.43                                                                              28.57                                                                              52.14                                                                              GeO.sub.2                                                                          5  159                                                                               90  -89                                           13  2.86                                                                              11.43                                                                              28.57                                                                              52.14                                                                              ZrO.sub.2                                                                          5  171                                                                               50  --*                                           14  2.86                                                                              11.43                                                                              28.57                                                                              52.14                                                                              SnO.sub.2                                                                          5  170                                                                               75  --*                                           15  2.86                                                                              11.43                                                                              28.57                                                                              52.14                                                                              CeO.sub.2                                                                          5  148                                                                               58  -190                                          16  2.86                                                                              11.43                                                                              28.57                                                                              52.14                                                                              HfO.sub.2                                                                          5  172                                                                               26  --*                                           __________________________________________________________________________      Note:                                                                          Sample Nos. 1-11: Examples of the present invention                            Sample Nos. 12-16: Comparative Examples                                        *Unmeasurable                                                            

As described above in detail, the dielectric ceramic composition of the present invention shows high εr and Q₀, and its τf can be widely controlled by adjusting the ratio of CaO/SrO, the amounts of Tl₂ O₃, Y₂ O₃ and MnO, and the amounts of GeO₂, ZrO₂, SnO₂, CeO₂ and HfO₂. It is highly suitable for microwave dielectric elements and temperature compensating capacitors, etc. 

What is claimed is:
 1. A dielectric ceramic composition consisting essentially of calcium oxide, strontium oxide, bismuth oxide and titanium oxide, and having a composition represented by the formula:

    (CaO).sub.a.(SrO).sub.b.(Bi.sub.2 O.sub.3).sub.c.(TiO.sub.2).sub.d

wherein 0≦a≦10, 5≦b≦15, 25≦c≦30, 50≦d≦60, and 5≦a+b≦20 by mol %.
 2. The dielectric ceramic composition according to claim 1, further consisting essentially of at least one of 5 weight % or less of thallium oxide, 5 weight % or less of yttrium oxide and 0.6 weight % or less of manganese oxide.
 3. A dielectric ceramic composition consisting essentially of calcium oxide, strontium oxide, bismuth oxide, titanium oxide and at least one of germanium oxide, zirconium oxide, tin oxide, cerium oxide and hafnium oxide, and having a composition represented by the formula:

    (CaO).sub.a.(SrO).sub.b.(Bi.sub.2 O.sub.3).sub.c.(TiO.sub.2).sub.d.(RO.sub.2).sub.e

wherein R represents at least one of Ge, Zr, Sn, Ce and Hf, and a, b, c, d and e satisfy 0≦a≦10, 5≦b≦15, 25≦c≦30, 50≦c≦60, 0≦e≦2 and 5≦a+b≦20 by mol %.
 4. A sintered ceramic article consisting essentially of greater than 0 to less than 10 mol % CaO, greater than 5 to less than 15 mol % SrO, greater than 25 to less than 30 mol % Bi₂ O₃, greater than 50 to less than 60 mol % TiO₂, the total content of CaO and SrO being greater than 5 but less than 20 mol %, said article having a quality factor under no load, Qo, of at least 100 and a temperature coefficient of resonance frequency, τf, measured between -20° C. and +60° C. of ±100 ppm/°C. 